Synergistic insecticidal compositions



United States Patent '6 2 990 323 'SYNERGISTIC INSEOTIOIDAL COMPOSITIONS Howard A. Jones and John A. Gar-man, Baltimore, Md., and Berton C. Dickinson, Lyndonville, N.Y.,' assignors the control of truck crop, forage crop and orchard insects.

The synergistic compositions of this invention can be formulated as aqueous emulsions, as dry or wettablc to Food Machinery and Chemical Corporation, New powders, as solutions or in any other suitable vehicle. York N- a cqrporafion P Delaware I The insecticidal compositions can be utilized as sprays, N0 gf f pp q 1955 as dusts, as Aerosol mixtures, insecticidal coating comgg' ggfagb and this apphcamm positions, and as residues. In general, they can be ap- Claims. (CL 167 30) plied by methods commonly used for control or eradica- 10 tion of insects, mites and the like. Thus these insec- This invention relates broadly to insecticidal compositicidal compositions can be formulated with solvents, tions, and more particularly to insecticidal compositions diluents and carrier media, adhesives, spreading, wetting containing 0,0-dimethyl O-(4-nitrophenyl) thiophosand emulsifying agents and other ingredients. phate and 4-methylumbelliferonyl N-ethylcarbamate. The relative proportions of the active ingredients as More Particularly, this invention relates to yn rgi i well as inert carriers, solvents, dispersants and the like insecticidal compositions of these compounds wherein may vary within wide limits. the insecticidal effectiveness of each component is en- Thus the relative proportion (ratio) of the Methyl hanced by the presence of the other to produce an un- Parathion to the carbamate ester can range from parts expected combined effect. of the former per 1 part of the latter to 1 part of the When two or more substances in combination show an 0 former per 40 parts of the latter and preferably about 1 unexpectedly high activity, as, for instance, insecticidal part of the former to about 5 parts of the latter. activity, the resulting phenomenon is called synergism. The quantities of the component toxicants in the final The mechanism of synergism is by no means understood. insecticidal compositions can range from 0.01% to It is, in fact, quite probable that it diifers with diflerent 25.00% for the Methyl Parathion and from 0.05% to synergistic combinations The term y g can be 50.00% for the carbamate, and preferably from 0.10% fi however, as a cooperative action hi s ento 10.00% for the Methyl Parathion and from 0.10% countered in combinations of two or more biologically acto 25 .00% for the carbamate. tive components in which the combined activity of the Th ro du e of the testing method are described two components exceeds the sum of the activities of the below, The details of the test experiments including the components when used alone. The insecticidal activity type of formulation and mode of ap lication or dosing, of the mixed components cannot be predicted from kn n and the species of insects which served as test subjects values of the individual components, but is unpredictable are given in the examples, and depends on the individual activity of neither. The test method used is described as follows:

It is an object of this invention to provide insecticidal compositions of enhanced killing power. Another object TURNTABLE METHOD of this invention is to produce novel compositions con- House flies-This method is described in the article, taining compounds capable of synergizing the knockdown Campbell and Sullivan, Soap and Sanitary Chemicals, 14 and killing properties of individual toxicants. A further (6); 119-425, 149 (1938). The tests were carried out object of this invention is to provide compositions includwith slight modifications from the method described in ing a relatively toxic phosphorus containing insecticide in the reference above. which superior insecticidal activity is obtained because Th t bl d i i d i h g towers, h of the Synergistic eflects, but which the ultimate toxicriod between spraying and actual exposure of settling mist ity to warm-blooded animals is greatly reduced because to the test ,fl is 6 Seconds, and fli are exposed to the of the lowef concentratlon? of P settling mist for 10 minutes. The sprayer is operated Rounds requlrefi when used combmanfm Wlth the rela at 5 p.s.i.g. Five milliliters of test solution are used for tlvely less toxic p i other objects fi each test. There is a filter paper placed in the bottom pi the mveiltlon become apparent mm t e of each test dish containing the house flies undergoing description of the invention set forth below. M rt H t d aft 24 h According to this invention, there are provided synertests a tyfoun S are ma 6 er ours gistic insecticidal compositions comprising 0,0-dimethyl The files used m these Fests were reared F to O-(4-nitrophenyl) thiophosphate, hereafter called Methyl siandard lilrocedmes estahhs'hed by the glenflcal i Parathion, and 4 methy1umbemfer0ny1 Nethylcarbamate' ties Manufacturers Association, as described 1n the article The synergistic insecticidal compositions of this inven- Pfiet Grady Method in the 1952 p B1116 Book- The tion may be used on a wide variety of insect and mite flies tested are 3 days old.

Table 1 \NCOORI Oarbamate Phosphate Mortality Test Test at 24 hrs. Cone. Conc. Method Subject (percent) R R (mgJ Name (mg./

100 ml.) 100 m1.)

ethyl 4-methylumbelllferonyL. 500 Turntable-u H0l1Seflie$--- 4 MethylParathlou. 10 do do 46 Do do d0 10 do -do 96 species, but are particularly eifective against house flies.

The combinations are highly effective and economical to use for such large-scale insecticidal requirements as This table illustrates the unexpected eifectiveness of insecticidal compositions of this invention against such insects as the house fly.

This application is a division of copending application Serial No. 496,596, filed March 24, 1955, now abandoned, which is a continuation-in-part of Serial No. 427,374, filed May 3, 1954, now abandoned.

We claim: t I

1. Synergistic insecticidal compositions comprising 0,0-dimethyl O-(4-nitrophenyl) thiophosphate and 4- methylumbelliferonyl N-ethylcarbamate, said components being employed in the ratio of about 1 part of said thiophosphate to about 5 parts of said carbamate ester.

2. The method of killing insects'w'hich comprises applying to the insects and their habitat a synergistic insecticidal composition comprising 0,0-dimethyl O-(4- nitrophenyl)thiophosphate and 4-methylumbelliferonyl N- ethylcarbamate, said components being employed in the ratio of about 1 part of said thiophosphate to about 5 parts of said carbamate ester.

4 *1 References Cited in the file of this patent UNITED STATES PATENTS Jelinek Apr. 11, 1950 Gysin May 25, 1954 OTHER REFERENCES Frear: Chemistry of the Pesticides, 3rd ed., January 1955, pp. 73-91. V 

2. THE METHOD OF KILLING INSECTS WHICH COMPRISES APPLYING TO THE INSECTS AND THEIR HABITAT A SYNERGISTIC INSECTICIDAL COMPOSITION COMPRISING O,O-DIMETHYL O-(4NITROPHENYL)THIOPHOSPHATE AND 4-METHYLUMBELLIFERONYL NETHYLCARBAMATE, SAID COMPONENTS BEING EMPLOYED IN THE RATIO OF ABOUT 1 PART OF SAID THIOPHOSPHATE TO ABOUT 5 PARTS OF SAID CARBAMATE ESTER. 